Chromium compounds of oxyanthraquinone sulfonic acids and process of making same.



UNITED STATES PATENT OFFICE.

RENE IBOHN, OF MANNHEIM, AND CARL IMMERHEISER, OF LUDWIGSHAFEN-ON-THE-' RHINE, GERMANY, ASSIGNORS TO BADISCHE ANILIN & SODA FABRIK, OF LUD- WIGSHAIFEN 0N-THE-RHINE, GERMANY, A CORPORATION.

CHROMIUM COMPOUNDs OF OXYANTHRAQUINONE SULFONIC ACIDS AND PROCESS OF MAKING SAME.

No Drawing.

To all whomit may concern:

Be it known that we, RENE BOHN and CARL IMMERHEISER, citizen of the Swiss Republic and subject of the King of Bavaria, residing, respectively, at Mannheim and Ludwigshafen-on-the-Rhine, Germany, have invented new and useful Improvements in Chromium Compounds of Oxyanthraquinone Sulfonic Acids and Processes of Making Same, of which the following is a specification.

In the specification of British Patent No. 1117 /7 8 it is stated that, by neutralizing the free alizarin sulfonic acid, or purpurin sulfonic acid, with chromium oxid, after carefully separating the mineral acid, soluble chromium salts can be obtained. We have now found that, by heating oxyanthraquinone sulfonic acids, under which term we also include salts and derivatives thereof, with chromium salts in the presence of water, we can obtain different and new compounds which are intensely colored and generally very easily soluble in water, so that they cannot be precipitated from their aqueous solutions by the additlon of indlfferent salts. They can be obtained, however, in the solid state, for instance by evaporation of the solution in cacao, or by the addition of certain organic agents (sue for instance as ethyl-alcohol) to the aqueous solutions. One molecular proportion of an oxyanthraquinone sulfonic acid can combine with varying quantities of chromium. The chromium salts obtainable according to the said British Patent No. 1117/7 8 can, for instance by treatment with chromium fiuorid, be converted into the productsof the present invention. The compounds obtainable according to this invention differ from the chromium salts obtained according to the said Patent No. 1117/78 in that the new compounds, on being applied to the vegetable fiber and steamed or treated with alkaline reagents, such for instance as ammonia, or sodium carbonate solution, or wlth damp ammoniacal fumes, give rise to strong blue-green to violet shades of excellent fastness against the action of Washing and light.

The new compounds can be employed Specification of Letters Patent.

Application filed December 3, 1912. Serial No. 734,697.

Patented Mar. 10, 1914.

either for the production of colorin matters, or of ink, and they are exceptionally useful for the production of color lakes, because they can be precipitated on to a substratum either at ordinary or at raised temperature, and either in the presence or absence of alkalis or agents having an alkaline reaction. Instead of precipitatin the already made chromium compoun in this manner, the oxyanthraquinone sulfonic acid, or a salt, or derivative, thereof, can be heated with a solution of a chromium salt in the presence of a substratum and then, if necessary, be precipitated by means of alkali or of an alkaline reacting agent, or of a mixture of both, either at ordinary or at raised temperature. The new color lakes thus obtained have valuable shades of color and are very fast. Particular valuable lakes are ob tainable from the chromium compound of hexa-oxyanthraquinone-disulfonic acid (acid alizarin blue BB).

The following are examples of how our invention can be carried into practical effect, but the invention is not confined to these examples. In Examples 1 and 2 the parts are by weight.

Example 1: Introduce 10 parts of the sodium salt of hexa-oxyanthraquinone-disulfonic acid into a solution of 20 parts of chromium fluorid in 600 parts of water, and heat the mixture until it boils. The color of the solution, which is at first reddish, becomes brilliant green-blue, and when the shade no longer, alters toward green the formation of the new compound is complete. If desired. the solution can be strongly evaporated without the chromium compound separating out. During the boiling, part of the hydrofluoric acid, which is set free, es

capes.

Instead of chromium fluorid, other chromium salt can be employed, such for instance as chrome alum, chromium chlorid and chromium formate, and in an analogous manner other oxyanthraquinone sulfonic acids, or salts or derivatives thereof, can be employed.

As concentrated acids are liable to affect the chromium compound, it is preferred, be-

fore evaporating the solution, to add a compound (such for instance as bisulfite) which has the power of fixing the acid.. NVhen chromium fiuorid is employed, the addition of silica, or the like, advantageous for this purpose. For instance, when commencing to evaporate down the solution obta ned according to the foregoing example, it 1s advantageous to add 2.5 parts of glass powder. 7

The following table gives some instances of the oxyanthraquinone sulfonic' acids which can be employed according to this invention, and the color of the solution of their chromium compounds in water Color of solution Chromium compound ofzgggggg g water.

1-Oxyanthraquinone-S-sulionic acid Red-violet. l-Oxyanthraquinone-dsulionic acid Orange-red. 1.2-Dioxyanthraquinonc-B-sulfonic acid. Yellowish red. 1.2-Dioxyanthraquinone-l-sulfonic acid. Orange-red. 1.2-l)ioxyanthraquinone-T-sulionic aci Carmine-red. 1.4-Dioxyanthraquinone 2-sulfonic aci 'Reddish blue. 1.4-Dioxyanthraquinone-G-sulfonic acid. Blue-violet. 1.5-Dioxyanth1aquinone-2.(i-disulfonic acid Carmine-red. 1.5-Dioxyanthraquinone-tetrasulfonlc acid. Red-violet. 4.8-1 )(i1nitro-1.5-dioxyanthraquinone-2.G-dlsulfonic Bluish red.

aci I 1.8-Dioxyanthraquinone-disull'onic acid Orange. 1.2.4-Trioxyanthraquinone-3-sulionic acid Red-violet 1.2.4-1rioxyanthraquinone-G-sulionic acid Bordeaux red. 1.2.5-Trioxyanthraquinonet-sulionic acid Violet-blue. 4-Nitro-1.5.8-trioxyanthraquinone-disulfonic acid. Blue-green. 1.4.7.S-Tetraoxyanthraquinone-sulfonic acid Reddish blue. 1.4.5.8-Tetraoxyanthraquinone-sulfonic acid Blue. 1.3.5. 7-Tetraoxyanthraquinone-sulfonic acid Yellow-red. Pentacyanin-monosulfouic acid Blue. Hexacyanin-monosulionio acid Greenish blue. Hexa-oxyanthraquinone-Z.G-disulfonic acid Green-blue. 41;-Iiiamigo-1.5-dioxyanthraquinone-monosu1- -B1uish green.

omc aei Example 2: Introduce, while stirring, the aqueous solution obtained according to the foregoing example into a substratum prepared from 200 parts of heavy spar, 100 parts of aluminium sulfate, 50 parts of calcined sodium carbonate and 120 parts of barium chlorid, and then, if necessary, heat the mixture or add a small quantity of sodium carbonate in order to fix the chro-.

mium compound. The color lake can be worked up in the usual manner and is of a pure blue-green color of excellent fastness against the action of light, and it also'has good covering power.

Other substrata are suitable for the purposes of this invention, for example zinc white, milk of lime, white lead, talc, fullers earth, lithopone, chrome yellow, or red lead, may be used.

In a similar manner, color lakes can be obtained from the other compounds obtainable as hercinbefore described and, if desired, the lakes can be produced'in the presence of Turkey red oil, or similar compound.

' Example 3: Prepare a printing paste from 200 grams of the solution obtained according to the foregoing Example 1, 500 grams of thickening (prepared from 4.4 grams of acetic acid, 66 grams of starch, 22 grams of glycerin, and 6.6 grams of gun tragaeanth) 40 grams of formic acid and 260 grams of water. Printthis on vegetable fiber, steam in the Mather-Plat apparatus for 5 minutes, wash with water and finish in the usual manner. A blue-green shade of excellent fastness against the action of wash ing and light is obtained. Instead of steaming, the printed material can be treated, for from 1 to 2 minutes, with a 3% solution of sodium carbonate, or with a solution containing 10 grams of 20% ammoniaper' liter, and then washed with water and finished in the usual manner.

The. following table gives someofthe shades obtainable in a similar manner from the chromium compounds of other oxyan thraquinone-sulfonic acids Chromium compound oi- Color of print.

1.2-Dioxyanthraquinone-3-sul fonic acid Red-brown. 1.2-Dioxyantliraquinone tsulfonic acid. 1 Brown. 1.2-Dioxyanthraquinone-7-sulionic acid Bluish Bordeaux 1.4-Dioxyanthraquinone-Z-sull'onic aci Black-green.

. Anthrarufin disulfonic acid Red-violet. Chrysazin disulionic acid Bordeaux. 1.2.5-Tnoxyanthraquinone- Rcddish blue.

' Alizarin Bordeaux sulfonic acid Blue.

1.4.5.8-Tetraoxyanthraquinone sulfonic acid Blue-green. Anthrachrysone disulfonic acid Red-brown. Pentacyanin mouosulfonic acid Blue-green. Hexacyanln monosulfonic acid Green. He aoxyanthraquinone-disulionic acid Blue-green.

4-Nit0-1.5.8etrioxyanthraquinone-2.(S disulionic Blue-green.

aci

Now what we claim is 1. The process of producing chromium compounds of oxyanthraquinone-sulfonic acids by heating an oxyanthraquinonesulfonic acid, with a chromium salt in the presence of water.

2. The process of producing a chromium compound of hexa-oxyanthraquinone-disulfonic acid by heating hexa-oxyant-hraquinone-disulfonic acid with chromium fiuorid in the presence of water.

3. The process of producing a chromium compound of hexa-oxyanthraquinone-disulfonic acid by heating hexa oxyanthraquinone-disulfonie acid with chromium iiuorid in the presence of water and of silicious material.

4-. As new articles of manufacture the compounds which can be obtained by heat ing an oxyanthraquinone-sulfonic acid with Lemme thraquinone-sulfonic acid residue and chroset our hands in the presence of two submlum, and whleh 1s soluble 1n water yleldscnblng wltnesses.

- ing a green-blue solution, but on being RENE B'OHN.

steamed in the presence of vegetable fiber CARL IMMERHEISER. 5 yields insoluble lakes giving green-b1ue Witnesses:

shades of excellent ifestness. J. Ame. Luna),

In testimony whereof We have hereunto JOSEPH FEIFFER. 

